recommendations on the transport of dangerous...

UNITED NATIONS

New York and Geneva, 2015

ST/SG/AC.10/11/Rev.6

Recommendations on the

TRANSPORT

OF

DANGEROUS GOODS

Manual of Tests and Criteria

Sixth revised edition

NOTE

The designations employed and the presentation of the material in this publication do not imply the

expression of any opinion whatsoever on the part of the Secretariat of the United Nations concerning the

legal status of any country, territory, city or area, or of its authorities, or concerning the delimitation of its

frontiers or boundaries.

ST/SG/AC.10/11/Rev.6

Copyright United Nations, 2015

All rights reserved.

No part of this publication may, for sales purposes, be reproduced, stored in a retrieval system or

transmitted in any form or by any means, electronic, electrostatic, magnetic tape, mechanical,

photocopying or otherwise, without prior permission in writing from the United Nations.

UNITED NATIONS PUBLICATION

Sales No.: E.15.VIII.3

ISBN 978-92-1-139155-8

eISBN 978-92-1-057567-6

ISSN 1014-7160

- 424 -

38.3 Lithium metal and lithium ion batteries

38.3.1 Purpose

This section presents the procedures to be followed for the classification of lithium metal and

lithium ion cells and batteries (see UN Nos. 3090, 3091, 3480 and 3481, and the applicable special

provisions of Chapter 3.3 of the Model Regulations).

38.3.2 Scope

38.3.2.1 All cell types shall be subjected to tests T.1 to T.6 and T.8. All non-rechargeable battery

types, including those composed of previously tested cells, shall be subjected to tests T.1 to T.5. All

rechargeable battery types, including those composed of previously tested cells, shall be subjected to tests

T.1 to T.5 and T.7. In addition, rechargeable single cell batteries with overcharge protection shall be

subjected to test T.7. A component cell that is not transported separately from the battery it is part of needs

only to be tested according to tests T.6 and T.8. A component cell that is transported separately from the

battery shall be subjected to tests T.1 to T.6 and T.8.

38.3.2.2 Lithium metal and lithium ion cells and batteries shall be subjected to the tests, as required

by special provisions 188 and 230 of Chapter 3.3 of the Model Regulations prior to the transport of a

particular cell or battery type. Cells or batteries which differ from a tested type by:

(a) For primary cells and batteries, a change of more than 0.1 g or 20% by mass,

whichever is greater, to the cathode, to the anode, or to the electrolyte;

(b) For rechargeable cells and batteries, a change in nominal energy in Watt-hours of

more than 20% or an increase in nominal voltage of more than 20%; or

(c) A change that would lead to failure of any of the tests,

shall be considered a new type and shall be subjected to the required tests.

NOTE: The type of change that might be considered to differ from a tested type, such that it might

lead to failure of any of the test results, may include, but is not limited to:

(a) A change in the material of the anode, the cathode, the separator or the electrolyte;

(b) A change of protective devices, including hardware and software;

(c) A change of safety design in cells or batteries, such as a venting valve;

(d) A change in the number of component cells;

(e) A change in connecting mode of component cells; and

(f) For batteries which are to be tested according to T.4 with a peak acceleration less

than 150 gn, a change in the mass which could adversely impact the result of the T.4

test and lead to a failure.

In the event that a cell or battery type does not meet one or more of the test requirements, steps shall be taken

to correct the deficiency or deficiencies that caused the failure before such cell or battery type is retested.

- 425 -

38.3.2.3 For the purposes of classification, the following definitions apply:

Aggregate lithium content means the sum of the grams of lithium content contained by the cells comprising a

battery.

Battery means two or more cells or batteries which are electrically connected together and fitted with devices

necessary for use, for example, case, terminals, marking or protective devices. Units which have two or more

cells that are commonly referred to as “battery packs”, “modules” or “battery assemblies” having the primary

function of providing a source of power to another piece of equipment are for the purposes of the Model

Regulations and this Manual treated as batteries. See definitions for "cell" and "single cell battery".

Button cell or battery means a round small cell or battery when the overall height is less than the diameter.

Cell means a single encased electrochemical unit (one positive and one negative electrode) which exhibits a

voltage differential across its two terminals, and may contain protective devices. See definitions for battery

and single cell battery.

Component cell means a cell contained in a battery. A component cell is not to be considered a single cell

battery.

Cycle means one sequence of fully charging and fully discharging a rechargeable cell or battery.

Disassembly means a vent or rupture where solid matter from any part of a cell or battery penetrates a wire

mesh screen (annealed aluminium wire with a diameter of 0.25 mm and grid density of 6 to 7 wires per cm)

placed 25 cm away from the cell or battery.

Effluent means a liquid or gas released when a cell or battery vents or leaks.

Fire means that flames are emitted from the test cell or battery.

First cycle means the initial cycle following completion of all manufacturing processes.

Fully charged means a rechargeable cell or battery which has been electrically charged to its design rated

capacity.

Fully discharged means either:

a primary cell or battery which has been electrically discharged to remove 100% of its rated

capacity; or

a rechargeable cell or battery which has been electrically discharged to its endpoint voltage as

specified by the manufacturer.

Large battery means a lithium metal battery or lithium ion battery with a gross mass of more than 12 kg.

Large cell means a cell with a gross mass of more than 500 g.

Leakage means the visible escape of electrolyte or other material from a cell or battery or the loss of material

(except battery casing, handling devices or labels) from a cell or battery such that the loss of mass exceeds

the values in Table 38.3.1.

Lithium content is applied to lithium metal and lithium alloy cells and batteries, and for a cell means the

mass of lithium in the anode of a lithium metal or lithium alloy cell, which for a primary cell is measured

when the cell is in an undischarged state and for a rechargeable cell is measured when the cell is fully

charged. The lithium content of a battery equals the sum of the grams of lithium content contained in the

component cells of the battery.

- 426 -

Lithium ion cell or battery means a rechargeable electrochemical cell or battery in which the positive and

negative electrodes are both intercalation compounds (intercalated lithium exists in an ionic or quasi-atomic

form with the lattice of the electrode material) constructed with no metallic lithium in either electrode.

A lithium polymer cell or battery that uses lithium ion chemistries, as described herein, is regulated as a

lithium ion cell or battery.

Mass loss means a loss of mass that exceeds the values in Table 38.3.2.2 below.

Table 38.3.1: Mass loss limit

Mass M of cell or battery Mass loss limit

M < 1 g 0.5%

1 g M 75 g 0.2%

M > 75 g 0.1%

NOTE: In order to quantify the mass loss, the following procedure is provided:

100M

MM (%) loss Mass

1

21

where M1 is the mass before the test and M2 is the mass after the test. When mass loss does not exceed the

values in Table 38.3.1, it shall be considered as "no mass loss".

Nominal energy or Watt-hour rating, expressed in watt-hours, means the energy value of a cell or battery

determined under specified conditions and declared by the manufacturer. The nominal energy is calculated

by multiplying nominal voltage by rated capacity expressed in ampere-hours.

Nominal voltage means the approximate value of the voltage used to designate or identify a cell or battery.

Open circuit voltage means the voltage across the terminals of a cell or battery when no external current is

flowing.

Primary cell or battery means a cell or battery which is not designed to be electrically charged or recharged.

Prismatic cell or battery means a cell or battery whose ends are similar, equal and parallel rectilinear figures,

and whose sides are parallelograms.

Protective devices means devices such as fuses, diodes and current limiters which interrupt the current flow,

block the current flow in one direction or limit the current flow in an electrical circuit.

Rated capacity means the capacity, in ampere-hours or milliampere-hours, of a cell or battery as measured by

subjecting it to a load, temperature and voltage cut-off point specified by the manufacturer.

NOTE: The following IEC standards provide guidance and methodology for determining the rated

capacity:

(1) IEC 61960 (First Edition 2003-12) : Secondary cells and batteries containing

alkaline or other non-acid electrolytes – Secondary lithium cells and batteries for portable applications;

(2) IEC 62133 (First Edition 2002-10): Secondary cells and batteries containing

alkaline or other non-acid electrolytes – Safety requirements for portable sealed secondary cells, and for

batteries made from them, for use in portable applications;

(3) IEC 62660-1 (First Edition 2011-01): Secondary lithium-ion cells for the propulsion

of electric road vehicles – Part 1: Performance testing.

- 427 -

Rechargeable cell or battery means a cell or battery which is designed to be electrically recharged.

Rupture means the mechanical failure of a cell container or battery case induced by an internal or external

cause, resulting in exposure or spillage but not ejection of solid materials.

Short circuit means a direct connection between positive and negative terminals of a cell or battery that

provides a virtual zero resistance path for current flow.

Single cell battery means a cell externally fitted with devices necessary for use in equipment or another

battery which it is designed to power, for example protective devices. See definitions for cell and battery.

NOTE: A single cell battery is considered a “cell” and shall be tested according to the testing

requirements for “cells” for the purposes of the Model Regulations and this Manual.

Small battery means a lithium metal battery or lithium ion battery with a gross mass of not more than 12 kg.

Small cell means a cell with a gross mass of not more than 500 g.

Type means a particular electrochemical system and physical design of cells or batteries.

Undischarged means a primary cell or battery that has not been wholly or partly discharged.

Venting means the release of excessive internal pressure from a cell or battery in a manner intended by

design to preclude rupture or disassembly.

Watt-hour rating, see Nominal energy.

38.3.3 When a cell or battery type is to be tested under this sub-section, the number and condition

of cells and batteries of each type to be tested are as follows:

(a) When testing primary cells and batteries under tests T.1 to T.5 the following shall be

tested in the quantity indicated:

(i) ten cells in undischarged states;

(ii) ten cells in fully discharged states;

(iii) four small batteries in undischarged states;

(iv) four small batteries in fully discharged states;

(v) four large batteries in undischarged states; and

(vi) four large batteries in fully discharged states.

(b) When testing rechargeable cells and batteries under tests T.1 to T.5 the following shall

be tested in the quantity indicated:

(i) ten cells at first cycle, in fully charged states;

(ii) four small batteries at first cycle, in fully charged states;

(iii) four small batteries after 50 cycles ending in fully charged states;

(iv) two large batteries at first cycle, in fully charged states; and

(v) two large batteries after 25 cycles ending in fully charged states.

- 428 -

(c) When testing primary and rechargeable cells under test T.6, the following shall be

tested in the quantity indicated:

(i) for primary cells, five cells in undischarged states and five cells in fully

discharged states;

(ii) for component cells of primary batteries, five cells in undischarged states and

five cells in fully discharged states;

(iii) for rechargeable cells, five cells at first cycle at 50% of the design rated

capacity; and

(iv) for component cells of rechargeable batteries, five cells at first cycle at 50% of

the design rated capacity.

(d) When testing rechargeable batteries or rechargeable single cell batteries under test T.7,

the following shall be tested in the quantity indicated:

(i) four small batteries at first cycle, in fully charged states;

(ii) four small batteries after 50 cycles ending in fully charged states;

(iii) two large batteries at first cycle, in fully charged states; and

(iv) two large batteries after 25 cycles ending in fully charged states.

Batteries or single cell batteries not equipped with battery overcharge protection that

are designed for use only as a component in another battery or in equipment, which

affords such protection, are not subject to the requirements of this test.

(e) When testing primary and rechargeable cells and component cells under test T.8, the

following shall be tested in the quantity indicated:

(i) ten primary cells in fully discharged states;

(ii) ten primary component cells in fully discharged states;

(iii) ten rechargeable cells, at first cycle in fully discharged states;

(iv) ten rechargeable component cells, at first cycle in fully discharged states;

(v) ten rechargeable cells after 50 cycles ending in fully discharged states; and

(vi) ten rechargeable component cells after 50 cycles ending in fully discharged

states.

(f) When testing a battery assembly in which the aggregate lithium content of all anodes,

when fully charged, is not more than 500 g, or in the case of a lithium ion battery, with

a Watt-hour rating of not more than 6 200 Wh, that is assembled from batteries that

have passed all applicable tests, one assembled battery in a fully charged state shall be

tested under tests T.3, T.4 and T.5, and, in addition, test T.7 in the case of a

rechargeable battery.

- 429 -

(g) When batteries that have passed all applicable tests are electrically connected to form

a battery in which the aggregate lithium content of all anodes, when fully charged, is

more than 500 g, or in the case of a lithium ion battery, with a Watt-hour rating of

more than 6 200 Wh, the assembled battery does not need to be tested if the assembled

battery is of a type that has been verified as preventing:

(i) Overcharge;

(ii) Short circuits; and

(iii) Over discharge between the batteries.

38.3.4 Procedure

Tests T.1 to T.5 shall be conducted in sequence on the same cell or battery. Tests T.6 and

T.8 shall be conducted using not otherwise tested cells or batteries. Test T.7 may be conducted using

undamaged batteries previously used in Tests T.1 to T.5 for purposes of testing on cycled batteries.

38.3.4.1 Test T.1: Altitude simulation

38.3.4.1.1 Purpose

This test simulates air transport under low-pressure conditions.

38.3.4.1.2 Test procedure

Test cells and batteries shall be stored at a pressure of 11.6 kPa or less for at least six hours

at ambient temperature (20 ± 5 °C).

38.3.4.1.3 Requirement

Cells and batteries meet this requirement if there is no leakage, no venting, no disassembly,

no rupture and no fire and if the open circuit voltage of each test cell or battery after testing is not less than

90% of its voltage immediately prior to this procedure. The requirement relating to voltage is not applicable

to test cells and batteries at fully discharged states.

38.3.4.2 Test T.2: Thermal test

38.3.4.2.1 Purpose

This test assesses cell and battery seal integrity and internal electrical connections. The test

is conducted using rapid and extreme temperature changes.


Test cells and batteries are to be stored for at least six hours at a test temperature equal to

72 ± 2 °C, followed by storage for at least six hours at a test temperature equal to - 40 ± 2 °C. The maximum

time interval between test temperature extremes is 30 minutes. This procedure is to be repeated until 10 total

cycles are complete, after which all test cells and batteries are to be stored for 24 hours at ambient

temperature (20 ± 5 °C). For large cells and batteries the duration of exposure to the test temperature

extremes should be at least 12 hours.

- 430 -






38.3.4.3 Test T.3: Vibration

38.3.4.3.1 Purpose

This test simulates vibration during transport.


Cells and batteries are firmly secured to the platform of the vibration machine without

distorting the cells in such a manner as to faithfully transmit the vibration. The vibration shall be a sinusoidal

waveform with a logarithmic sweep between 7 Hz and 200 Hz and back to 7 Hz traversed in 15 minutes.

This cycle shall be repeated 12 times for a total of 3 hours for each of three mutually perpendicular mounting

positions of the cell. One of the directions of vibration must be perpendicular to the terminal face.

The logarithmic frequency sweep shall differ for cells and batteries with a gross mass of not

more than 12 kg (cells and small batteries), and for batteries with a gross mass of more than 12 kg (large

batteries).

For cells and small batteries: from 7 Hz a peak acceleration of 1 gn is maintained until 18 Hz

is reached. The amplitude is then maintained at 0.8 mm (1.6 mm total excursion) and the frequency increased

until a peak acceleration of 8 gn occurs (approximately 50 Hz). A peak acceleration of 8 gn is then maintained

until the frequency is increased to 200 Hz.

For large batteries: from 7 Hz to a peak acceleration of 1 gn is maintained until 18 Hz is

reached. The amplitude is then maintained at 0.8 mm (1.6 mm total excursion) and the frequency increased

until a peak acceleration of 2 gn occurs (approximately 25 Hz). A peak acceleration of 2 gn is then maintained

until the frequency is increased to 200 Hz.



no rupture and no fire during the test and after the test and if the open circuit voltage of each test cell or

battery directly after testing in its third perpendicular mounting position is not less than 90% of its voltage

immediately prior to this procedure. The requirement relating to voltage is not applicable to test cells and

batteries at fully discharged states.

38.3.4.4 Test T.4: Shock

38.3.4.4.1 Purpose

This test assesses the robustness of cells and batteries against cumulative shocks.


Test cells and batteries shall be secured to the testing machine by means of a rigid mount

which will support all mounting surfaces of each test battery.

- 431 -

Each cell shall be subjected to a half-sine shock of peak acceleration of 150 gn and pulse

duration of 6 milliseconds. Alternatively, large cells may be subjected to a half-sine shock of peak

acceleration of 50 gn and pulse duration of 11 milliseconds.

Each battery shall be subjected to a half-sine shock of peak acceleration depending on the

mass of the battery. The pulse duration shall be 6 milliseconds for small batteries and 11 milliseconds for

large batteries. The formulas below are provided to calculate the appropriate minimum peak accelerations.

Battery Minimum peak acceleration Pulse duration

Small batteries

150 gn or result of formula

*

100850)(

massgonAccelerati n

whichever is smaller

6 ms

Large batteries

50 gn or result of formula

*

30000)(

massgonAccelerati n

whichever is smaller

11 ms

* Mass is expressed in kilograms.

NOTE: IEC Standard 60068-2-27 (Fourth Edition 2008-02): Environmental testing-Part

2-27: Tests – Test Ea and guidance: Shock provides guidance on tolerance for acceleration and pulse

duration.

The relationship between minimum peak acceleration and mass is illustrated in Figure

38.3.4.1 for small batteries and Figure 38.3.4.2 for large batteries.

- 432 -

Figure 38.3.4.1: Relation between the Peak Acceleration and the Mass

for small batteries (below 12.0 kg).

Figure 38.3.4.2: Relation between the Peak Acceleration and the Mass

for large batteries (equal or above 12.0 kg).

Each cell or battery shall be subjected to three shocks in the positive direction and to three

shocks in the negative direction in each of three mutually perpendicular mounting positions of the cell or

battery for a total of 18 shocks.

- 433 -






38.3.4.5 Test T.5: External short circuit

38.3.4.5.1 Purpose

This test simulates an external short circuit.


The cell or battery to be tested shall be shall be heated for a period of time necessary to reach

a homogeneous stabilized temperature of 57 ± 4 °C, measured on the external case. This period of time

depends on the size and design of the cell or battery and should be assessed and documented. If this

assessment is not feasible, the exposure time shall be at least 6 hours for small cells and small batteries, and

12 hours for large cells and large batteries. Then the cell or battery at 57 ± 4 °C shall be subjected to one

short circuit condition with a total external resistance of less than 0.1 ohm.

This short circuit condition is continued for at least one hour after the cell or battery external

case temperature has returned to 57 ± 4 °C, or in the case of the large batteries, has decreased by half of the

maximum temperature increase observed during the test and remains below that value.

The short circuit and cooling down phases shall be conducted at least at ambient

temperature.


Cells and batteries meet this requirement if their external temperature does not exceed

170 °C and there is no disassembly, no rupture and no fire during the test and within six hours after the test.

38.3.4.6 Test T.6: Impact/Crush

38.3.4.6.1 Purpose

These tests simulate mechanical abuse from an impact or crush that may result in an internal

short circuit.

38.3.4.6.2 Test procedure – Impact (applicable to cylindrical cells not less than 18.0 mm in diameter)

NOTE: Diameter here refers to the design parameter (for example the diameter of 18 650 cells is

18.0 mm).

The test sample cell or component cell is to be placed on a flat smooth surface. A

15.8 mm ± 0.1 mm diameter, at least 6 cm long, or the longest dimension of the cell, whichever is greater,

Type 316 stainless steel bar is to be placed across the centre of the sample. A 9.1 kg ± 0.1kg mass is to be

dropped from a height of 61 ± 2.5 cm at the intersection of the bar and sample in a controlled manner using a

near frictionless, vertical sliding track or channel with minimal drag on the falling mass. The vertical track or

channel used to guide the falling mass shall be oriented 90 degrees from the horizontal supporting surface.

The test sample is to be impacted with its longitudinal axis parallel to the flat surface and

perpendicular to the longitudinal axis of the 15.8 mm ± 0.1 mm diameter curved surface lying across the

centre of the test sample. Each sample is to be subjected to only a single impact.

- 434 -

38.3.4.6.3 Test Procedure – Crush (applicable to prismatic, pouch, coin/button cells and cylindrical

cells less than 18.0 mm in diameter)

NOTE: Diameter here refers to the design parameter (for example the diameter of 18 650

cells is 18.0 mm).

A cell or component cell is to be crushed between two flat surfaces. The crushing is to be

gradual with a speed of approximately 1.5 cm/s at the first point of contact. The crushing is to be continued

until the first of the three options below is reached.

(a) The applied force reaches 13 kN ± 0.78 kN;

Example: The force shall be applied by a hydraulic ram with a 32 mm diameter piston

until a pressure of 17 MPa is reached on the hydraulic ram.

(b) The voltage of the cell drops by at least 100 mV; or

(c) The cell is deformed by 50% or more of its original thickness.

Once the maximum pressure has been obtained, the voltage drops by 100 mV or more, or the

cell is deformed by at least 50% of its original thickness, the pressure shall be released.

A prismatic or pouch cell shall be crushed by applying the force to the widest side. A

button/coin cell shall be crushed by applying the force on its flat surfaces. For cylindrical cells, the crush

force shall be applied perpendicular to the longitudinal axis.

Each test cell or component cell is to be subjected to one crush only. The test sample shall be

observed for a further 6 h. The test shall be conducted using test cells or component cells that have not

previously been subjected to other tests.


Cells and component cells meet this requirement if their external temperature does not

exceed 170 °C and there is no disassembly and no fire during the test and within six hours after this test.

38.3.4.7 Test T.7: Overcharge

38.3.4.7.1 Purpose

This test evaluates the ability of a rechargeable battery or a single cell rechargeable battery to

withstand an overcharge condition.


The charge current shall be twice the manufacturer's recommended maximum continuous

charge current. The minimum voltage of the test shall be as follows:

(a) when the manufacturer's recommended charge voltage is not more than 18 V, the

minimum voltage of the test shall be the lesser of two times the maximum charge

voltage of the battery or 22 V.

(b) when the manufacturer's recommended charge voltage is more than 18 V, the

minimum voltage of the test shall be 1.2 times the maximum charge voltage.

Tests are to be conducted at ambient temperature. The duration of the test shall be 24 hours.

- 435 -


Rechargeable batteries meet this requirement if there is no disassembly and no fire during

the test and within seven days after the test.

38.3.4.8 Test T.8: Forced discharge

38.3.4.8.1 Purpose

This test evaluates the ability of a primary or a rechargeable cell to withstand a forced

discharge condition.


Each cell shall be forced discharged at ambient temperature by connecting it in series with a

12V D.C. power supply at an initial current equal to the maximum discharge current specified by the

manufacturer.

The specified discharge current is to be obtained by connecting a resistive load of the appropriate size and

rating in series with the test cell. Each cell shall be forced discharged for a time interval (in hours) equal to

its rated capacity divided by the initial test current (in ampere).


Primary or rechargeable cells meet this requirement if there is no disassembly and no fire

during the test and within seven days after the test.

38.4 Substances evolving flammable vapour

38.4.1 Purpose

This section of the Manual presents the test procedure to determine whether during handling,

transport and storage substances of Class 9 evolving flammable vapours (see UN No. 2211), are able to

evolve a dangerous concentration of flammable vapours in closed containers resulting in the formation of a

flammable atmosphere and, as a consequence, have to be classified or not.

38.4.2 Scope

The scope of the test method is to determine whether polymeric beads with encapsulated

blowing agent, fulfilling the description of UN No. 2211, need not to be classified under these UN numbers.

38.4.3 Classification procedure for substances liable to evolve flammable vapours

Polymeric beads with encapsulated blowing agent shall be tested according to the procedures

below to determine whether classification under UN No. 2211 is needed.

38.4.4 Test U 1: Test method for substances liable to evolve flammable vapours

38.4.4.1 Introduction

The ability to evolve flammable vapours is determined by placing the substance in a

hermetically closed glass bottle, at a specified temperature for a prescribed period of time, and then,

determine the identity and concentration of flammable vapours.

recommendations on the transport of dangerous...

Documents